CH691102A5 - Poison baits for controlling harmful insects. - Google Patents

Abstract

Bait for controlling harmful parasites, partic. insects, comprising an active 1-arylpyrazole deriv. of formula (I), is based on a substance which forms a gel upon hydration. R1 = CN, methyl or halo; R2 = S(O)nR3, 4,5-dicyanoimidazol-2-yl or haloalkyl; R3 = alkyl or haloalkyl; R4 = H, halo, NR5R6, S(O)mR7, C(O)R7, C(O)OR7, alkyl, haloalkyl OR8 or N=C(R9)(R10); R5, R6 = H, alkyl, haloalkyl, C(O)alkyl, alkoxycarbonyl or S(O)rCF3; or R5+R6 = alkylene (opt. interrupted by one or more heteroatoms e.g. O or S); R7 = alkyl or haloalkyl; R8 = H, alkyl or haloalkyl; R9 = H or alkyl; R10 = phenyl or heteroaryl (opt. substd. by one or more halo or by one -OH, -O-alkyl, -S-alkyl, cyano or alkyl); R11, R12 = H, halo, CN or NO2; R13 = halo, haloalkyl, haloalkoxy, S(O)qCF3 or SF5; X = trivalent N or C-R12, the three C valences forming part of an aromatic nucleus; m, n, q = 0-2; r is not defined; provided that if R1 = Me, then either R3 = haloalkyl, R4 = NH2, R11 = Cl, R 13 = CF3 and X = N; or R2 = 4,5-dicyanoimidazol-2-yl, R4 = Cl, R11 = Cl, R13 = CF3 and X = =C-Cl.

Description

         

  



  The invention relates to poisoned baits for controlling harmful insects.



  The invention wishes to make available to users poisoned baits for the fight against harmful insects, having excellent attractive and baiting properties as well as high efficiency against various insects which it is desired to control by the use of baits. attractive.



  The invention relates to attractive baits which can be used to control harmful parasites, and in particular insects, consisting of a gelling agent by hydration and containing as active material a 1-arylpyrazole derivative of general formula (I):
EMI1.1
 
 
 



  in which:



  R1 represents a CN or methyl radical or a halogen atom;



  R2 represents S (O) nR3 or a 4,5-dicyanoimidazol 2-yl or haloalkyl radical;



  R3 represents an alkyl or haloalkyl radical;



  R4 represents hydrogen, or a halogen atom, or a radical chosen from the following radicals: NR5R6, S (O) mR7, C (O) R7, C (O) OR7, alkyl, haloalkyl, OR8 and N = C (R9) (R10);



  R5 and R6 independently of one another represent a hydrogen atom or an alkyl, haloalkyl, C (O) alkyl, alkoxycarbonyl or S (O) rCF3 radical; or R5 and R6 can together form a divalent alkylene radical which can be interrupted by one or more divalent heteroatoms such as oxygen or sulfur;



  R7 represents an alkyl or haloalkyl radical;



  R8 represents an alkyl or haloalkyl radical or a hydrogen atom;



  R9 represents an alkyl radical or a hydrogen atom;



  R10 represents a phenyl or heteroaryl radical which may optionally be unsubstituted or substituted by one or more halogen atoms or a radical chosen from the following radicals: -OH, -O-alkyl, -S-alkyl, cyano, and alkyl;



  R11 and R12 represent, independently of one another, hydrogen or a halogen atom, or a CN or NO2 radical,



  R13 represents a halogen atom or a haloalkyl, haloalkoxy, S (O) qCF3 or SF5 radical;



  X represents a trivalent nitrogen atom or a C-R12 radical, the other three valences of the carbon atom being part of the aromatic nucleus;



  m, n and q represent, independently of each other, an integer equal to 0, one or two;



  provided that, if R1 represents a methyl radical, then either R3 represents a haloalkyl radical, R4 represents NH2, R11 represents CI, R13 represents CF3 and X represents N; or if R2 represents a 4,5-dicyanoimidazoly 2-Yl radical, R4 represents CI, R11 represents CI, R13 represents CF3, and X represents = C-CI.



  The alkyl radicals generally contain from 1 to 6 carbon atoms.



  A preferred group of 1-arylpyrazoles according to the invention is that in which:



  R1 represents CN; R3 represents a haloalkyl radical; R4 represents NH2; X represents C-R12;



  R11 and R12 represent, independently of one another, a halogen atom; and



  R13 represents a haloalkyl radical.



  A particularly preferred compound is 5-amino-1- (2,6-dichloro-4- (trifluoromethylphenyl) -4-trifluoromethylsulfinyl-3-cyanopyrazole, designated by "compound (A)", in the following description. compound (A) can be prepared by the methods described in European patent application A-0 295 117.



  The compounds of general formula (I) can be prepared according to known methods, for example those described in international patent applications N <os> WO 87/3 781, 93/6 089, and 94/21 606 as well as in European patent applications 295,117, 403,300, 385,809 or 679,650, the German patent application 19,511,269 and US patents N <os> 5,232,940 and 5,236,938 or by other methods known to man skilled art in chemical synthesis, particularly through the publications made in the Chemical Abstract and in the literature to which these works refer. The compositions containing the compounds of general formula (I) can also be prepared according to the methods of the prior art or according to similar methods.



  The following products can be used, for example, as gelling agent according to the invention: Gellan gum, carrageenan gum, agar agar, gelatin, locust bean gum, xanthan gum, jelutong gum. These gelling agents can be used alone or as a mixture of two or more, in any relationship with one another. Gellan gum is the preferred gum. Gellan gum is a natural polysaccharide isolated from Pseudomonas Elodea cultures and contains glucose, glucoronic acid and rhamnose. It is also marketed under the registered trademark Kelcogel of Kelco Company. The patents relating to Gellan gum were published in Japanese patent applications S59-88,051 filed May 21, 1984 (food compositions), S60-11,501 filed January 21, 1985 (unheated gel gum).



  The invention also relates to a process for the preparation of poisoned baits which comprises the preparation of a liquid composition containing the gelling agent, water and a compound of general formula (I), then the solidification of the liquid composition to form a gel. The hydrating gelling agent can be prepared, for example, by mixing a gelling agent and water, making the mixture liquid by heating to a temperature usually between 40 and 90 DEG C and solidifying it by cooling.



  The poisoned baits usable according to the invention, for controlling harmful parasites, for example, insects, can for example, be prepared by mixing the gelling agent and water, making the mixture liquid by heating, and adding the compound of general formula (I), as well as for example an attractant, a baiting substance, or other adjuvants if necessary, and by solidifying it by cooling. The products thus obtained can be formulated in any desirable form by placing them in a suitable mold during the cooling and solidification process. They can further be put into any form by methods including cutting, grinding, etc., after solidification.



  The ratio between the gelling agent and the water is generally between 0.001: 99.999 and 50:50.



  The attractive baits for controlling harmful parasites, for example insects, according to the present invention generally contain an attractive substance and a baiting substance. As baiting substance, there may be mentioned for example, cereal powders such as wheat powder, corn powder, rice powder, rice bran, etc., starches such as potato starch , corn starch, etc., sugars such as maltose, arabinose, galactose, lactose, sorbitose, glucose, molasses, honey, etc., and glycerin, etc.

   As an attractive substance, there may be mentioned, for example, fatty acids such as caprylic acid, caproic acid, capric acid, lauric acid, oleic acid, etc., higher alcohols such as octyl alcohol , dodecyl alcohol, oleic alcohol, etc., and flavors such as onion flavor, milk flavor, butter flavor, etc.



  The attractive baits for combating harmful insects, in accordance with the present invention may contain, as other adjuvant agents, a stabilizing substance, a repellant for species which one does not want to see devouring the baits, a coloring substance, an agent antiseptic, etc. As stabilizing agent, it is possible, for example, to cite a calcium salt such as calcium lactate, calcium chloride, etc. As a repellant, mention may be made, for example, of pungent or bitter substances such as guinea pepper powder, dinatonium benzoate, etc. As coloring agents, mention may be made, for example, of Red N DEG 2, Red N DEG 102, Yellow N DEG 4, Yellow N DEG 5, caramel, etc.

   As antiseptic agents, there may be mentioned, for example, sorbic acid, sorbinates, esters of paraoxybenzoic acid, etc.



  In the attractive baits for combating harmful parasites, for example insects, in accordance with the present invention, the content of compound of general formula (1) is generally between 1 × 10 <-> <5> and 50% in w / w, the content of gelling agent is generally between 1 x 10 <-> <3> and 99.99% in w / w, the content of attracting and baiting agents is generally between 1 x 10 < -> <3> and 99.99% and the content of other adjuvants between 0 and 99.99% w / w.



  In addition, the attractive baits for combating harmful parasites, for example insects, may contain, in addition to the compound of general formula (1), other active insecticidal substances.



  The attractive baits for the control of harmful parasites, for example insects, in accordance with the present invention can be used in industry or in agriculture to control different insects by placing them in the premises or live or on the premises. passage, harmful insects, either in the form of poisoned bait alone, or by placing them in suitable containers.



  Among the harmful parasites liable to be destroyed, mention may be made not only of insects such as cockroaches and in particular German cockroaches (Blatella germanica), smoky brown cockroaches (Periplaneta fuliginosa), flies such as house flies, ants such as Formica fusca japonica, Tetramorium cacspitum, Lasius niger, Monomorium pharanois, Crematogaster laboriosa, Pristomyrmex pungens, Monomorium nipponense, Pheidole nodus, Brachyponcra chinensis, Camponotus japonicus, Iridomyrmex itoi, ant ant, ant ant, ant and in particular crustaceans such as armidillidia and in particular Armidillidium vulgare etc.

   Although the doses of poisoned baits usable for controlling harmful parasites, for example insects, may vary depending on the target species, the conditions in which they occur, etc., it may however be indicated that the doses of fipronil to be used in industry or in agriculture are, for example, between 1 × 10 <-> <4> and 500 mg (w / w) in the case of applications in houses for the control of cockroaches , and between 1 x 10 <-> <4> and 500 mg (w / w) per application site, in the case of applications made outdoors against ants or against, Armadillidia.



  The present invention can be explained in more detail by a few examples of applications.



  The examples which follow are examples of preparations of formulations which can be used according to the invention.


 Preparation example 1
 



  1 g of Gellan gum and 68.7 g of water were mixed and then heated to 80-90 DEG C with stirring to give a homogeneous solution; 0.1 g of compound (A) and 0.2 g of calcium lactate were then added with stirring, then 30 g of honey still with stirring; the mixture obtained was poured into a cylinder 3.0 cm in diameter, cooled and solidified to give poisoned bait.


 Preparation example 2
 



  Attractive baits for the control of harmful insects can be prepared by the same method as that described in Preparation example 1, with the only exception that 0.01 g of compound (A) was used instead of 0.1 g.


 Preparation example 3
 



  Attractive baits for combating harmful insects can be prepared by the same method as that described in Preparation example 1, with the only exception that 0.001 g of compound (A) was used instead of 0, 1 g.



  The following examples are examples of tests.


 Test example N DEG 1
 



  A wooden cage, water, solid food and poisoned bait were placed in an acrylic resin container (25 cm x 25 cm x 10 cm); 90 adult females of German cockroaches were then introduced.



  The number of dead German cockroaches has been counted periodically. The results are given in Table 1.



  In addition, and by way of comparison, the results obtained with poisoned baits (Comparison example 1) prepared by mixing 0.1 g of fipronil, 30 g of honey, 20 g of mashed potato and 10 g of bran of rice, are also given in Table 1.
<tb> <TABLE> Columns = 4 Table 1
<tb> Head Col 1: Time
<tb> Head Col 2 to 4 AL = L: Number of dead insects
<tb> Head Col 2: (hours)
<tb> Head Col 3: Preparation example 1
<tb> Head Col 4: Preparation example 2
<tb> Head Col 5: Comparison example 1
<tb> <SEP> 6 <SEP> 62 <SEP> 44 <SEP> 20
<tb> <SEP> 9 <SEP> 83 <CEL AL = L> 80 <CEL AL = L> 51
<tb> <SEP> 12 <SEP> 88 <SEP> 84 <SEP> 68
<tb> <SEP> 24 <SEP> 90 <SEP> 89 <SEP> 80
<tb> <CEL AL = L> 27 <SEP> 90 <SEP> 80
<tb> <SEP> 30 <SEP> 82
<tb> <SEP> 48 <SEP> 88
<tb> <SEP> 72 <CEL CB = 4 AL = L> 90
<tb> </TABLE>


 Test example N DEG 2
 



  A wooden cage, water, solid food and poisoned bait were placed in an acrylic resin container (25 cm x 25 cm x 10 cm); 30 adult females of smoked brown cockroaches (Periplaneta fuliginosa) were then introduced.



  The number of dead smoked brown cockroaches was counted periodically. The results are given in Table 1.



  In addition, and for comparison, the results obtained with poisoned baits (Comparison example 1) prepared by mixing 0.1 g of compound (A), 30 g of honey, 20 g of mashed potato and 10 g of rice bran, are also given in table 2.
<tb> <TABLE> Columns = 4 Table 2
<tb> Head Col 1: Time
<tb> Head Col 2 to 4 AL = L: Number of dead insects
<tb> Head Col 2: (hours)
<tb> Head Col 3: Preparation example 1
<tb> Head Col 4: Preparation example 2
<tb> Head Col 5: Comparison example 1
<tb> <SEP> 9 <SEP> 22 <SEP> 1 <SEP> 0
<tb> <SEP> 12 <SEP> 24 <CEL AL = L> 7 <CEL AL = L> 1
<tb> <SEP> 24 <SEP> 28 <SEP> 26 <SEP> 15
<tb> <SEP> 30 <SEP> 30 <SEP> 27 <SEP> 15
<tb> <CEL AL = L> 48 <SEP> 27 <SEP> 21
<tb> <SEP> 72 <SEP> 30 <SEP> 25
<tb> <SEP> 96 <SEP> 27
<tb> </TABLE>


 Test example N DEG 3
 



  A wooden cage, water, solid food and poisoned bait were placed in a plastic container (the bottom of which was 9 cm in diameter); 60 adults of Pristomyrmex pungens were then introduced.



  The number of dead insects (Pristomyrmex pungens) was counted periodically. The results are given in Table 3.
<tb> <TABLE> Columns = 4 Table 3
<tb> Head Col 1: Time
<tb> Head Col 2 to 4 AL = L: Number of dead insects
<tb> Head Col 2: (hours)
<tb> Head Col 3: Preparation example 1
<tb> Head Col 4: Preparation example 2
<tb> Head Col 5: Comparison example 1
<tb> <SEP> 24 <SEP> 51 <SEP> 43 <SEP> 7
<tb> <SEP> 48 <SEP> 60 <CEL AL = L> 58 <SEP> 20
<tb> <SEP> 72 <SEP> 60 <SEP> 52
<tb> <SEP> 96 <SEP> 60
<tb> </TABLE>


 Test example N DEG 4
 



  A certain amount of soil, a case of porcelain, water, cabbage leaves, and poisoned bait were placed in an acrylic resin container (25 cm x 25 cm x 10 cm); 50 adults of Armadillidium vulgare were then introduced.



  The number of dead insects (Armadillidium vulgare) was counted periodically. The results are given in Table 4.
<tb> <TABLE> Columns = 3 Table 4
<tb> Head Col 1: Time
<tb> Head Col 2 to 3 AL = L: Number of dead insects
<tb> Head Col 2: (hours)
<tb> Head Col 3: Preparation example 1
<tb> Head Col 4: Preparation example 2
<tb> <SEP> 1 <SEP> 21 <SEP> 24
<tb> <SEP> 2 <CEL AL = L> 40 <SEP> 39
<tb> <SEP> 3 <SEP> 46 <SEP> 45
<tb> <SEP> 4 <SEP> 49 <SEP> 46
<tb> <SEP> 5 <CEL AL = L> 50 <CEL AL = L> 48
<tb> <SEP> 6 <SEP> 50
<tb> </TABLE>



  As can be seen, on reading the various results of the tests, the attractive baits for combating harmful insects, in accordance with the present invention give excellent effectiveness in controlling the various harmful parasites, for example, insects. Furthermore, as can be seen from the results of the comparison examples, the poisoned baits according to the invention have a much better efficacy than that of the reference formulations containing the same amount of the material [compound of general formula (1) ].



  The attractive baits for the fight against harmful parasites, for example, insects, in accordance with the present invention give an excellent effectiveness for fighting the various harmful parasites for example, insects.


      

Claims (9)

  1. An attractive bait usable for controlling harmful parasites, and in particular insects, comprising a hydrated agent and an active material, characterized in that it is constituted as the basic substance of an agent gelling by hydration, and containing as active ingredient a compound of general formula (l): EMI11.1          in which:    R1 represents a CN or methyl radical or a halogen atom;    R2 represents S (O) nR3 or a 4,5-dicyanoimidazol 2-yl or haloalkyl radical;    R3 represents an alkyl or haloalkyl radical;    R4 represents hydrogen, or a halogen atom, or a radical chosen from the following radicals:  NR5R6, S (O) mR7, C (O) R7, C (O) OR7, alkyl, haloalkyl, OR8, and N = C (R9) (R10);    R5 and R6 independently of one another represent a hydrogen atom or an alkyl, haloalkyl, C (O) alkyl, alkoxycarbonyl or S (O) rCF3 radical; or R5 and R6 can together form a divalent alkylene radical which can be interrupted by one or more divalent heteroatoms such as oxygen or sulfur;    R7 represents an alkyl or haloalkyl radical;    R8 represents an alkyl or haloalkyl radical or a hydrogen atom;    R9 represents an alkyl radical or a hydrogen atom;    R10 represents a phenyl or heteroaryl radical which may optionally be unsubstituted or substituted by one or more halogen atoms or by a radical chosen from the following radicals: -OH, -O-alkyl, -S-alkyl, cyano, and alkyl ;      R11 and R12 represent, independently of one another, hydrogen or a halogen atom, or a CN or NO2 radical,    R13 represents a halogen atom or a haloalkyl, haloalkoxy, S (O) qCF3 or SF5 radical;    X represents a trivalent nitrogen atom or a C-R12 radical, the other three valences of the carbon atom being part of the aromatic nucleus;    m, n, r and q represent, independently of each other, an integer equal to 0, one or two;    provided that, if R1 represents a methyl radical, then either R3 represents a haloalkyl radical, R4 represents NH2, R11 represents Cl, R13 represents CF3 and X represents N; or if R2 represents a 4,5-dicyanoimidazoly 2-Yl radical, R4 represents CI, R11 represents CI, R13 represents CF3, and X represents = C-CI. 2.  A bait according to claim 1 in which:    R1 represents CN; R3 represents a haloalkyl radical; R4 represents NH2; X represents C-R12;    R11 and R12 represent, independently of one another, a halogen atom; and    R13 represents a haloalkyl radical. 3. A bait according to claim 1 wherein the compound of general formula (1) is 5-amino-1- (2,6-dichloro-4- (trifluoromethylphenyl) -4-trifluoromethylsulfinyl-3-cyanopyrazole. 4. A bait according to claim 1 wherein the parasites are insects. 5. A bait according to any one of the preceding claims, in which the gelling agent is Gellan gum. 6. A bait according to one of claims 1 to 5 wherein the ratio between the gelling agent and water is between 0.001: 99.999 and 50:50 by weight. 7.  A bait according to one of claims 1 to 6 which contains between 1 x 10 <-> <5> and 50% of a compound of general formula (1) in wt / wt, between 1 x 10 <-> <3 > and 99.99% of gelling agent in w / w, from 1 x 10 <-> <3> to 99.99%, in w / w of attractive or baiting agent, and between 0 and 99.99% other adjuvants. 8. A method of preparing a poisoned bait according to one of claims 1 to 7 characterized in that it comprises  the preparation of a liquid composition containing a gelling agent, water and a compound of general formula (l) according to the definition of claim 1 and  - Solidification of the liquid composition to give a gel. 9. A process for controlling pests in industry or in agriculture, characterized in that a poisoned bait according to one of claims 1 to 7 is used.